Aromatic polyepoxide treated derivatives of alkylene oxide-amine modified phenolic-resins, and method of making same



Unite AROMATIC POLYEPOXEDE TREATED DERIVA- TIVES F ALKYLENE (PXIDE-AMINE MODIFIED gHENOLIC-RESHJS, AND METHOD OF MAKING Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware 4 Claims. (Cl. 26045) The present invention is a division of our copending application Serial No. 350,532, filed April 22, 1953.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

Attention is directed to two co-pending De Groote applications, Serial No. 310,552, filed September 19, 1952, and Serial No. 333,387, filed January 26, 1953. These two applications describe hydrophile products obtained by the oxyalkylation of the condensation product of certain phenol-aldehyde resins with respect to hydroxylated secondary monoamines and formaldehyde.

The present invention is concerned with a method of reacting said oxyalkylated derivatives of the kind just described with a phenolic polyepoxide of the kind previously described in our aforementioned co-pending application, Serial No. 305,079.

Thus the present invention is concerned with products of reaction obtained by a 3-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic hydroxylated secondary monoamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain monoepoxides, hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain phenolic polyepoxides, hereinafter described in detail, and cogenerically associated compounds formed in their preparation.

A more limited aspect of the present invention is concerned with products of reaction wherein the oxyalkylated resin condensate is reacted with a member of the class of compounds of the following formula:

in which R represents a divalent radical including ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom; the divalent radical the divalent States Patent 2,854,430 Patented Sept. 30, 1958 radical, the divalent sulfone radical, and the divalent gen atom from the phenol in which R, R", and R'" represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms.

A further limited aspect of the invention is represented by the products wherein the oxyalkylated resin condensate is reacted with a member of the class consisting of (a) compounds of the following formula wherein R is essentially an aliphatic hydrocarbon bridge, each n independently has one of the values 0 to 1, and

R is an alkyl radical containing from 1 to 4 carbon atoms, or even 12 carbon atoms, and (b) cogenerically associated compounds formed in the preparation of (a) preceding, including monoepoxides.

Reference herein to being thermoplastic or non-thermosetting characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting .with the monoepoxide-derived product. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, Will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, Where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxy rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane- (l,2,3,4 diepoxy butane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it. becomes obvious the reaction can take place with any oxyalkylated phenol-aldehyde resin condensate by virtue of the fact that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondary amino group. In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an oxyaikfiated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

.4 methanol mixture, for instance, 5% to 10% of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

The polyepoxide-treated condensates obtained in the manner described are, in. turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

For purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those products which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconate or the acetate or hydroxy acetate, have suflicien-tly hydrophile character to at least meet the test set in which the various characters have their previous significance and the characterization oxyalkylated condensate is simply an abbreviation for the oxyalkylated condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their Weight of 5% glueonic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xyleneforth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into ten parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated secondary monoamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides;

Part 7 is concerned with the oxyalkylation of the products described in Part 6, preceding;

Part 8 :is concerned with reactions involving the two preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more than a reaction between two moles of a previously prepared oxyalkylated amine-modified phenolaldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 10 is concerned with uses for the products herein described either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide group per molecule. for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co-generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weight the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present.

Thus,

6 Indeed, the mixture can be prepared free from monomers and still be satisfactory. 'Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances Where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our pref-' erence is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4, 4' isomers predominating and with lesser quantities of the 2, 2 and 4, 2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with cpoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, What is said hereinafter, although directed to one class or a few classes, applies with equal force and eifect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfurcontaining compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example,

the use of epichlorohydrin or glycerol dichlorohydrin. A number of problems are involved in attempting to produce these materials free from cogeneric materials of related composition.

For a discussion of these difficulties, reference is made to U. S. Patent No. 2,819,212,

beginning at column 7, line 21.

included for purpose of illustration.

These particular compounds are described in the two patents just mentioned.

TABLEI Ex- Patent ample Diphenol Dlglycidyl Ether Retar- Number once 1A CH:(C5H4OH)2 D1(epoxypropoxyphenybmethane 2, 505,486 2A OH:OH(CH4OH)1.- Di(epoxypropoxyphenyl)methylmethanc. 2,506,486 3). (CH3)O(CH4OH); Di(epoxypropoxyphenyl)dimethylmethane... 2, 500,480 4A C2H5C(CH3)(CQH4OH)1.. Di(epoxypropoxyphenyl)cthylmethylmethane 2,506,486 5A (C2H5)IC(C5H4OH)2--.-- Di(epoxypropoxyphenyl)dlethylmethane 2,506,480 6A CH C3H7 C5H4OID2 Di(eopxypropoxyphenyl)methylpropylmethane. 2, 500,486 7A CH3 (CQH5)(C3 H); D1(epoxypropoxyphenyDmethylphenylmethane" 2,505,485 8A C H O(CiH5)(OiH40H)i Di(epoxypropoxyphenyl)ethylphenylmethane..- 2, 506,486 9A C;H C(G H )(G H OH) Di(epoxypropoxyphenyhgropyl hen lmethane 2,503,486 10A 4 0C( a 5)( 6H40 )1 Di(epoxypropoxyphenyl) uty p eny ethane- 2,506,486 11A. (CHH4 GH(C5H4OH)2 Di(epoxypropoxyphenyl)tolylmethane 2,506,486 12A (CH OQHOOUJHQ)(CGH4OH) Di(epoxypr0poxyphenyl)tolylmethylmethanc 2,506,486 BA"..- Dihydroxy diphcnyl 4,4-bis(2,3-epoxypropoxy)dlphenyl 2,530,353 14A (CH3)C(C4H5.C@H3OH)1 2,2-bis(4-(2,3-ep0xypr0poxy)Z-tertlarybutylphenyl))propanc.. 2, 530,353

PART 3 Subdivision B Subdivision A The preparations of the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl others, have been described in a number of patents. For convenience, reference will be made to two only, to Wit, 30 examples can be specified by reference to the formula aforementioned U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

As to the preparation of low-molal polymeric epoxides or mixtures reference is made to aforementioned U. S. Patents Nos. 2,575,558 and 2,582,985.

light of U. S. Patent No. 2,575,558, the following therein provided one still bears in mind it is in essence an over-simplification.

I OH

(in which the characters have their previous significance) Example -R1O from HRXOH R- n n Remarks number B1 Hydroxy benzene CH; 1 0,1,2 Phenol known as bishenol A. Low polymeric mixture a at $5 or more C where n=0, remainder largely where l 'n=1, some where n=2. CH;

B2 do CH; 1 O, 1, 2 Phenol known as bis-phenol B. See note (I; regarding B1 above. e CH:

B3 Orthobutylphenol cm 1 0,1,2 Even though it is preferably 0, yet the l usual reaction product might well 0on- C- teln materials where n is 1, or to a 6 lesser degree 2.

134 Orthoamylphenol CH; 1 0,1,2 Do.

B5 Orthooctylphenol (EH; 1 0,1,2 Do.

B6 Orthononylphenol (EH; 1 0,1,2 Do.

JJH.

B7 Orthododecylphenol (3H1 1 0,1,2 Do.

I; CH3

B8 Metaeresol CH; 1 0,1,2 See prior note. This phenol used as (g initial material is known as bis-phenol C. For other suitable bis-phenols lee $3. U. S. Patent 2,564,191.

Example R O from HR OH R n n Remarks number B9 MetocresoL- CH; 1 0, 1, 2 See prior note.

B10 Dibutyl (ortho-para) phenol. H 1 0, 1,2 Do.

B11 Diamyl (ortho-para) phenol- 13 1 0,1,2 D0.

B12 Dioctyl (ortho-para.) phenol- H 1 0, 1, 2 Do.

B13 Dinonyl (ortho-para) phenol- H 1 0, 1, 2 Do.

B14 Diamyl (ortho-para) phenol. H 1 0, 1, 2 Do.

3 I CH;

15 do H 1 0, 1, 2 D0.

3 B (il'gHs B16 Hydroxy benzene 0 1 0,1,2 D0.

1 g Dianlyl phenol (ortho-paro). S- S- 1 0, 1, 2 Do.

do --S 1 0,1,2 Do.

Dibutylpheuol (ortho-para). g 1% 1 0,1,2 Do.

B20 do H H 1 0,1,2 D0.

B21 Dinonylphenol(ortho-para). lg lg 1 0, 1,2 Do.

B22 Hydroxy benzene g 1 0, 1,2 Do.

B23. do None -1 0 0,1,2 D0.

B24 Ortho-isopropyl phenol CH 1 0,1,2 See priornote. (As to preparation of 4,4-

isopropylidene bis-(2isopropylphenol) see U. S. Patent No. 2,482,748, dated I Sept. 27, 1949, to Dietzler.) CH5 B25 Para-octyl phenol --CH -SOH 1 0,1, 2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et a1.)

B26 Hydroxybenzene 1. CH3 1 0, 1, 2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. 2,526,545.)

iii: l C2 5 Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

7 Similar phenols which are monofunctional, for instance,

paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other samples include:

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R; is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

CIHHOCHPOCSHH CsHu CsHn in which the --C H groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

i'h n 1 13 See U. S. Patent No. 2,285,563.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH R: R! f R1 CH3 H "12 wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R, is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See

U. S. Patent No. 2,515,906.

CH=CH O\ OH C=CH OH H]C-?CH1 HIC(IJGH;

CH1 CH1 See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

(IJIHn CIHH OH OH See U. S. Patent No. 2, 331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as Alkyl R y Alkyl Alkyl in which R is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH CH3 CH3 OH in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximately in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional' phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. .These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted inthe 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxyl'ated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R R R '14 The basic nonhydroxylated amine may be designated thus:

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas: I

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few lOths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For puraasgeso '15 poses of .convenience suitable resins are characterized in the following table:

TABLE 111 M01. wt

Ex- R' of resin ample R Position derived 1; molecule number of R from- (based on n+2) Tertiary butyl Para..." Formal- 3. 5 882.5

Secondary butyL..- Ortho... 3. 5 882. 5 Tertiary amyl Para- 3. 5 959. 5 Mixed secondary Ortho... 3. 5 B05. 5

and tertiary amyl. Propyl 3. 5 805.5 3. 5 1,036. 5 3. 5 l, 190. 5 3. 5 1, 267. 5 3.5 1,344. 5 3. 5 1,498. 5 Tertiary but-yl 3.5 945. 5

Tertiary amyl 3.5 1,022. 5 N v1 3. 5 1, 330. 5 3. 5 l, 071. 5

15a Tertiary amyl 3.5 1,148.5 1641 Nonyl 3. 5 1, 456. 5 17a Tertiary butyl 3. 5 1,008.5

1841 Tertiary amyl 3. 5 1,085. 5 19a NOnyl 3. 5 1, 393. 5 20a Tertiary butyl 4. 2 996. 6

21a Tertiary amyl 4. 2 1, 083. 4 22a onyl 4. 2 1,430. 6 23a Tertiary butyl 4.8 1, 094. 4 Ma Tertiary amyl 4.8 1,189.6 25a Nonyl 4.8 1, 570. 4 26a Tertiary amyl 1. 5 604. Hexyl 1. 653. 0 l. 5 688. 0

35a Amyl do do 2.0 692.0 3641 Hexyl do. o 2.0 748.0

PART 5 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamine whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designed by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ dicthanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchlo' ride, esters of chloroacetic acid, alkyl bromides, dimethylsulfate, esters of sulfonic acid, etc., so as to convert the primary amine into a secondary amine. Among others, such amines include Z-amino-l-butanol, 2-amino-2-methyl-l-propanol, 2-amino-2-methyl 1,3 propanediol, 2- amino-2-ethyl-1,3-propanediol, and trie(hydroxymethyl)- 'aminomethan'e. Another example of such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Similarly, one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. The preparation of such amines or suitable reactants for preparing them has been described in the literature and particularly in two United States patents, to wit, U. S. Patents Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CIHJO C$H4O 021140 CrHtOCJLC] Such haloalkyl ethers can be reacted with ammonia or with a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a secondary amine in which there is not only present a hydroxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following formulas:

(041100 CH2CH(CH.|) 0 (CH:)CHCHI) NH HO CzH (CHsO CHzCHgO CH1CH O CHsCHs) NH HOC:H4

(CHrO CHaCHsCHsCHgCHsCHg) HO 01H;

or comparable compounds having two hydroxylated groups of different lengths as in no orncmo cmonio omen.

no 61H ass 1,430

Other suitable amines may be illustrated by CH3 noonm romon NH HO.CH2.([).CH2OH CH3 onafxonzon NH CHmlCHzOH See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic aminonitrogen atom can be obtained from any suitable alcohol or the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann. Among the reactants described in said latter patent are the following:

CEr-CH-CHr-NH-CHz-(OHOH)rCHgOH PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as diiferentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since'manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of. subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher tempera tures, for instance, ordinary room temperature. Thus,

we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or simi lar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the'liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or Water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt'form.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stir ring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature, then the amount of unreacted 19 formaldehyde is decreasedsubsequently and makes it easier toprevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refiuxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could 'be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example, 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is, then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale it there is any ditficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, forinstance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking,'such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as onecan reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of timewhich avoids loss of amine or formaldehyde. At a higher temperature we use a phaseseparating trap and subjectthe mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde, and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the. usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is. another index.

In light of what has been said previously, little more need be said as to the actual procedure e ployed. for the preparation of the herein; described condensation products. The following example. will. serve by way of illustration.

Example 1 b The phenol-aldehyde resin is the one that has been identified previously as Example In. It was obtained from a para-tertiary butylphcnol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end-v of the reactions The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which exeludesthe 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6; overall nuclei. The resin so obtained ina neutral: state had a light amber color. 7

8.82 grams of the resin identified as la preceding were powdered and mixed with 700. grams xylene. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to-3 5 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously. and formaldehyde added slowly. The formaldehyde used was a 37% solutionand 160- grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 2l= hours. At

the end of this period of time it; was refluxed, using aphase-separating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed .to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phaseseparating'trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part. of the xylene was removed until the temperature reached about C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or a tacky resin. The overall reaction time was a little over 30 21 hours.- In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours. Note that in Table IV following there are a large mixture yielded a clear solution by the time the bulk' of thewater, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table IV.

TABLE IV Strength of Reac Reac- Max. Ex. Resin Amt., formal- Solvent used tion tlon dis- N 0. used gm. Amine used and amount e y and temll, time, till.

soln. and 0. (hrs) temp.,

amt. 0.

1b. 1a. 882 Dlethanolamine, 210 grams 37%, 162 g... Xylene, 700 g. 22-26 32 137 2b 3a 480 Dlethanolamlne, 105 grams 37%, 81 g. Xylene, 450 gm. 21-23 28 150 3b Ban". 633 do Xylene, 600 g 20-22 36 145 4b In"... 441 Dipropanolamine, 133 grams 30%, 100 g Xylene, 400 2 20 3 34 146 5b 3a 480 do do. Xylene, 450 g. 21-23 24 141 6b 8a 633 do Xylene, 600 gm. 21-28 24 145' 7b 1a. 382 Ethylethanolamlne, 178 grams. Xylene, 700 g... 20-26 21 152 Sb..- 3a 480 Ethylethanolamine, 89 grams Xylene, 450 gm. 24-30 28 151 9b 8a 633 o do Xylene, 600 g 22-25 27 147 10b-- l1a 473 Cyclohexylethanolamine, 143 grams. 30%, 100 g... Xylene, 450 2... 21-31 31 146 l1b 1211.--. 511 do 37%, 81 g d0 22-23 36 148 12b l3a 665 do d0 Xylene, 550 g... -24 27 152 C2H5OC2H4OC2H4 136--.- 1a 441 NH, 176 grams do Xylene, 400 g. 21-25 24 150 HOG- H CzHsOOnHQOCzH] 14b 3a 480 NH, 176 grams .d0 Xylene, 450 g 20-26 26 146 OIHEOOlHAOOZHL 150-... 7a. 695 N H, 176 grams d0 Xylene, 550 gm. 21-27 147 noolntoolmocam 166--.. 1a.-... 441 H, 192 grams --d0 Xylene, 400 g.... 20-22 30 148 HOOzH.

HOC2H4OC2H4002H4 17b---. 311"--- 480 NH, 192 grams do do 20-25 28 150 HO OgH4O (EH 02H4 18b ML... 511 NH, 192 grams d0 Xylene, 500 g 21-24 32 149 HOCzH4OCaH4OO2 4 19b 20a 498 NH, 192 grams do Xylene, 450 g. 22-25 32 153 HOC2H4 CH2(OC2H4)3 206.-.. 2111-..- 542 NH, 206 grams 30%, 100 g.-- Xylene, 500 g.... 21-23 36 151 HOC2H4 CHa(OC2H4)a 2117.... 23m... 547 NH, 206 grams" do 25-30 84 148 HOCIH4 226 1a.- 441 NH, 206 grams .d0 Xylene, 400 g 22-23 31 146 236.... 244L 595 Decylethanolamine, 201 grams 37%, 81 g.. Xylene, 500 gm. 22-27 24 i 145 246---. 2511.--- 391 Deeylethanolamine, 100 grams 30%, g. Xylene, 300 gm. 21-25 26 147 number of added examples illustrating the same proce- PART 7 dure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C. or thereabouts. Usually the In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 6, we have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. The oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. The oxyalkylation step is carried out in a manner which is sub.- stantially conventional for the oxyalkylation of compounds having labile hydrogen atoms, and for that reason '23 a detailed descriptionof the procedure is omitted and the process w'fll simply be illustrated by the following examples:

Example The oxyalkylation-susceptible compound employed is the one previously described and designated as Example 1b. Condensate 1b was in turn obtained from diethanolamine and the resin previously identified as Example 1a. Reference to Table III shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 11.16 pounds of this resin condensate were dissolved in 7 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 135 C., and at a pressure of about -to pounds.

The time regulator was set so as to inject the ethylene oxide in approximately two hours and then continue stirring for a half-hour or longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the. comparatively :high concentration of catalyst. T h amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 11.16 pounds. This represented a molal ratio of moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2232. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also fior the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is includedin the data, or subsequent data, or in the data presented in tabular form in subsequent Tables V and VI.

The size of the autoclave employed was 25 gallons.

In innumerable comparable oxy'alkylations 'I have -withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and-subjected to oxyalkylation with a different oxide.

Example 2c This example simply illustrates the further oxyalkylavarious stages being based on the addition of this .particular amount. Thus, at the endof the oxyethylation step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1. The theoretical molecular weight was 3348.

The maximum temperature during the operation was 130 C. to 135 C. The maximum'pressure was in the range of 15 to 20 pounds. The time period was one hour.

Example 3c The oxyalkylation proceeded in the same manner decribed in Examples la and 26. There was no added solvent and no added catalyst. The oxide added was 11.16 pounds and the total oxide at the end of the oxyethylation step was 33.48 pounds. The molal ratio of oxide to condensate was 76.2 to 1. f Conditions as far as temperature and .pressure and time were concerned were all the time as in Examples 1c and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example .4:

The oxyethylation was continued and the amount of oxide added again was 11.16 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at'the end of the reaction period was 5580. The molal ratio of oxide to condensate was 101.6 to '1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 3% hours. The reaction unquestionably began to slow up somewhat.

Example 5 c The oxyethylation continued with the introduction of another 11.16 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic 'soda'was added. The theoretical molecular weight at the end of the agitation period was 6696, and the molal ratio of oxide to resin condensate was 127 to 1. The time period, however, dropped to 1% hours. Operating temperature and pressure remained the same as in the previous example. Exarrrple 6c The same procedure was followed as in the "previous examples except' tha't an added A pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 11.16 pounds, bringing-the total oxide introduced to"66.'96 pounds. The temperature and pressure during this period were the same as before. There was no added catalyst and also no added solvent. The time period was 2% hours.

Example 70 The same procedure was. followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 78.12 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8928. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 3 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 89.28 pounds. The theoretical molecular weight was 10,044. The molal ratio of oxide 'to resin condensate was 203.2 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous examples is employed in connection with :a. number of the other condensates described previously; All these *data have been presented in tabular'form in a series of four tables, Table III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in someinstances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autocalve. ,This is immaterial but happened to 'be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Table V and VI, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 410 through. 800 were obtainedby the 'use ofpropylene oxide alone.

25 Thus, in reference to Table V it is to be noted as follows.

The example number of ea-.:h compound is indicated in the first column.

26 ployed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

The identity of the oxyalkylation-susceptible com- Column 11 shows the catalyst at the end of the repound, to Wit, the resin condensate, is indicated in the action period. second column. Column 12. shows the amount of solvent at the end of The amount of condensate is shown in the third the reaction period. column. Column 13 shows the molal ratio of ethylene oxide to Assuming that ethylene oxide alone is employed, as condensate. happens to be the case in Examples 16 through 40c, the Column 14 can be ignored for the reason that no proamount of oxide present in the oxyalkylation derivatives pylene oxide was employed. 1s shown in column 4, although in the initial step since Referring now to Table VHI. It 1s to be noted that the no oxide is present there is a blank. first column refers to Examples 10, 2c, 30, etc.

When ethylene oxide is used exclusively the 5th col- The second column gives the maximum temperature umn is blank. employed during the oxyalkylation step and the thlrd The 6th column shows the amount of powdered caustic column gives the maximum pressure. soda used as a catalyst, and the 7th column shows the The fourth column gives the time per1od employed. amount of solvent employed. The last three columns show solubility tests by shaking The 15th column shows the theoretical molecular a small amount of the compound, including the solvent weight at the end of the oxyalkylation period. present, with several volumes of water, xylene and kero- The 8th column states the amount of condensate pressene. It sometimes happens that although xylene 1n coment in the reaction mass at the end of the period. paratively small amounts will dissolve in the concentrated As pointed out previously, in this particular series the material, when the concentrated material in turn is diamount of reaction mass withdrawn for examination was luted with xylene, separation takes places. so small that it was ignored and for this reason the resin Referring to Table VI, Examples 410 through 800 are condensate in column 8 coincides with the figure in the counterparts of Examples 10 through c, except that column 3. the oxide employed is propylene oxide instead of ethylene Column 9 shows the amount of ethylene oxide emoxide. Therefore, as explained previously, two columns 30 are blank, to wit, columns 4 and 9.

TABLE v Composition before Composition at end Molal ratio M0160. Ex. No. wt.

0-5 0-8 Ethl. Pro 1. Cata- Sol- O-S Ethl. Propl. Qatar 501- Ethyl. Propl. based cmpd., cmpd., oxide, 0x1 6, lyst, vent, empd., oxide, oxide, lyst, vent, oxide oxide on theex.No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. s. lbs. lbs. to oxyto oxyoretical alkyl. alkyl. value an nnpi- 11 went cmpd. cmpd.

'Oxyalkylatlon-susceptible.

'TA BLI .VI

Composltlonibelore Composition-at end Mold ratio u I Ex. No. wt.

08 048' mm]. Propl. iCata-i 801- i O-B' Ethl. Pro I. Cate- Sol- Ethyl. Pro 1. based ernpd., ornpd., oxide, oxide, lyst, .7 went, .ompd.,- oxide, or! 0, lie vent, oxide oxl e v on theex. No lbs lbs. lbs. lbs. lbs. lbs. lbs. lbs. I s. lbs. to oxyto oxforetical 1 1 alky alky value 1. .eusoe empd. emp

11.16 1.1 7.0, 11.16 11.16 1.1 7.0' 19.3 2, 232 :11. 16 1 11 6 I 1.1 7. .0 11.16 22.32 1. 1 7.1) t 38. 6 3,346 11. 16 22.32 1. 1 7.0., '11. 16 33. 48 1. 1 7. 57. 8 4, 464 '11. '16 33:48" 1.1 7:0" 11.16 44. 64 .1. 1 7. 0 77.0 5, 580 11.16, 44.64 LL13 7:01 11.16 55.80 1.1 7.0 96.5 7 12 11.16 55.80 1. 4 7. 0 11. 78. 12 l. 4 7. 0 117. 8 10, 044 11. '16 78.12 1. 4 '7. 0 1 1'. 1'6 100. 44 l. 4 7. 0 180. 5 12, 276 11. 16 100.244 21.4 1 '7. 0 1.1.16 122.76 1. 4 7.0 m 0 13,362 12.50 1.1, 4.5 12.50 12.50 1.1 4.5 21.6 am 12350 12. 5 i 1.1 '45 12:50 25. [II 1. 1 4.5 43. 21 3, 750 12:50 25. 0 'l.'1 .4. 55 12:50 37. 50 1. 1 4. 5 .64.,8. 5,0 12.50 37. 5 1. 1 4.5, 50 50. (I) 1. l 4. 5 86. 4 6,250 12. 50 50:1) 1. -1 4. 5 12.5) 62.50 1. 1 4. '5 108. 0 8, 750 12. 50 v 62.5 1.5, 4. 5'. 12:50:, 87. 50 1.5 4. 5 '151. 2. 11, 250 12.50 87. 5 1. 5 ,4. 5 12. 50 112. 50 1.5 4. 5 .1. 4 13, 750 L2. 50 112.5 1.5 4.5 1 12. 50 137. so 1. 5 4. 5 237. 6 15, (I!) 10.-84; 1.1 7.0 I 10.34 10. 84 1. 1 1 7. 0 1B. 7 2,166 10.84 I 10.84 1.1 v 7. 0 10.84 21. 68 1.1 7. 0 37. 4 3, 252 10.84 21.68 1 1. 1 7:0 I 10.84" 32. 52 1.1 7. 0; 56. 1 4, 336 110.84 32.52 1. 1 7. 01 10.84 43. 36 1. 1 7:0 .74. 8 5, m 10. 84 B. 36 1.1 f7. 0' 10. 84 54. 1.1 7.0. 93.5 7, 588 10.84 54. 20 1. 5 7.26 111584 75.38 '1. 5 7.0 no. 9 9, 756 10. 84 15.88: 1.5 7.0 10.84 p 97. 56 1.5; 7:0 I 168.3 11,224 10.84 117. 56 1. 5 7.'0 10.84 119. 24 1. 5 7. 0 205. 7 13, 008 12..56 1. 2. 4.5 12356 12. 56 1. 2 4. 5 21. 7 2, 512 512. 56. 12.56 1.2, -.4.5' 12.as- 25.12. 1.2, 4.5, $14; 3,768 12. 56 '25. 12 1. 2 4'. 5 12.56 37. 68 1. 2 4. 5 65. 1 5, 024 12. 56 37.568 I 1.2 b5 12556 50. 24 1. 2 4. 5 86. 8 6, 280 -12. 56 50. 24 l. 2 4. 5 12. 56 62. 80 1. 2 4. 5 108. 4 8, 792 12. 56 52. 80 1. 5 4. 5 12. 56 87. 92 1. 5 4. 5 151. 9 11, 304 12. 56 87. 92 1. 5 4. 5 12. 56 113. 04 l. 5 4. 5 195. 3 13, 816 12. 56 113. 04 1. 5 4. 5 12. 56 138. 16 1. 5 4. 5 238. 7 15, 072 11. 16 1. 1 7. 0 11. 16 5. 58 1. 1 7. 0 9. 6 1, 674 11. 16 5. 58 1. 1 7. 0 11. 16 11. 16 1. 1 7. 0 19. 2 2, 232 11. 16 11. 16 1. 1 7. 0 11. 16 16. 74 1. 1 7. 0 2s. 8 2, 790 11.16 16.74 1. 1 7.0- 11.15 22.32 1.1 7.0 38. 4 3,348 11. 16 22. 32 1. 1 7. 0 -11.16 27. 90 l. 1 7. 0 48. 0 3, 906 ll. 16 27.90 1.4- 7.0 11:16; 38% 1.4 7.0 76.2 5,022 11. 16 I 39. 06- 1. 4 7. 0 11. 16} 50. 22 1. 4 7.-0 86. 4i 6, 138 11. 16 50.22 l. 4 7. 0 11. 16 61. 38 1.4 '7. 0 105. 6 7, 254

Oxyalkylatlon-susceptible.

Reference is now made to Table VH. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through .and including 32d. They are derived,

in .turn, from compounds in the .c

oxide afterward. Inversely, those compounds obtained" from 530 and 62c obviously came from aprior series in which propylene oxide was used first.

rln the preparation of this series indicated by thesmall.

letter =d, as 1d, 2d, 3d, etc., the initial "0 series such as 35c, 39c, 53c, and 620, were duplicated and the 'oxyalkylation stopped at the point designated instead of being carried further as may have beeii'the. case :in the; original oxyalkylation step. Then oxyalkylation -pr'oceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, andethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be.

noted that the :initial product, i. e., 350, consisted of the reaction product involving 11.16 pounds of the resin condensate, 16.74 pounds of ethylene oxide, 1 pound of caustic soda, and 7.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table 7 VII refers to the total amount of catalyst, i. e., the catalyst present from thefirst oxyalkylation step plus added cata-- lyst, if any. The same is true in regard to the solvent.

Reference to the solvent refers'to the total solventpresent, i. e., that from the first oxyalkylation step-plus added solvent, if any.

In thisieries, ittwill be noted that the theoretical molec- :ular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the .endof one step is tbevalue-at the beginning of the next step, except obviously at rthe very start the value depends on the theoretical molecular weightat the end of the initial oxyalkylationstep; i. e., oxyethylation for 1d through 16d, and oxypropylation for'17d through 32d.

It willv be noted also that .under the rnolal ratio the values of both oxides tothe resin condensate are included.

The data .given in regard to the operating conditions is substantially the same as before and appears in Table The productsyresulting from theseprocedures may contain modestamounts, or havesmall amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such'distillation also may re- ;move traces or small amounts of-uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and :then go back to propylene oxide; 'or, one could use a combination in which butylene oxide is-used along witheither one of the two oxides just mentioned, or a combination 4% both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no eifort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching or some other industrial uses, there is no justification for the cost of bleaching the product. 1

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen atom, the removal of the alkaline catalyst is somewhat more difiicult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda chars, etc. As far as use in demulsificauon 1s concerned, 15 P TABLE VII Composition before Oomposltlon at 9nd Molal ratio Molec. Ex. No. wt.

-8 0-8 Ethl. Propl. Cata- 801- 0-8" Ethl. Propl. Cata- Sol- Ethyl Propl. based cmpd,, cmpd oxide, xide, lyst, vent, 0mpd., oxide, oxide, lyst, vent, oxide oxide on theex. N0. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretical alkyl alkyl value snscept suscept. cmp cmpd 350---. 11.1 16.74 1.0 7.0 11.16 16.74 5.58 1.0 7.0 38.0 9.63 3,348 2% 356---. 11.12 16.74 58 1.0 7.0 11.16 16.74 11.16 1.0 7.0 38.0 19.26 3,906 3d 35c 11.16 16.74 11.16 1.0 7.0 11.16 16.74 16.74 1.0 7.0 38.0 28.9 4,464 4d 35c. 11.16 16.74 16.74 1.0 7.0 11.16 16.74 22.32 1.0 7.0 38.0 38.5 5,022 5d 35c 11.16 16.74 23.32 1.0 7.0 11.16 16.74 27.90 1.0 7.0 38.0 48.15 5,580 6d 35c 11.16 16.74 27.90 1.0 7.0 11.16 16.74 33.48 1.5 7.0 38.0 57.75 6,138 74. 35L- 11.16 16.74 33.48 1.5 7.0 11.16 16.74 39.06 1.5 7.0 38.0 67.4 6,696 8d. 35c 11.16 16.74 39.06 1.5 7.0 11.16 16.74 44.64 1.5 7.0 38.0 77.0 7,253 911 390-... 11.16 39.06 1.3 7.0 11.16 39.06 5.58 1.3 7.0 89.0 9.6 5,022 10d 390-..- 11.16 39.06 5.58 1.3 7.0 11.16 39.06 11.16 1.3 7.0 89.0 19.2 5,580 1111 390---- 11.16 39.06 11.16 1.3 7.0 11.16 39.06 16.74 1.3 7.0 89.0 28.8 6,138 1241 390-- 11.16 39.06 16.74 1.3 7.0 11.16 39.06 22.32 1.3 7.0 89.0 38.4 6,696 13d 39c 11.16 39.06 22.32 1.3 7.0 11.16 39.06 27.90 1.8 7.0 89.0 48.1 7,254 14d 390-. 11.16 39.06 27.90 1.8 7.0 11.16 39.06 19.06 1.8 7.0 89.0 67.3 8,370 1511 390-- 11.16 39.06 39.06 1.8 7.0 11.16 39.06 50.22 1.8 7.0 89.0 86.5 9,486 16d 39c- 11.16 39.06 50.22 1.8 7.0 11.16 39.06 61.38 1.8 7.0 89.0 105.7 10,602 17d 530--.- 12.5 62.5 1.1 4.5 12.5 6.25 62.5 1.1 4.5 14.2 108 9,375 1811 53c 12.5 6.25 62.5 1.1 4.5 12.5 12.50 62.5 1.1 4.5 28.4 108 10,000 19d 530-..- 12.5 12.50 62.5 1.1 4.5 12.5 18.75 62.5 1.1 4.5 42.6 108 10,625 2011 530-.-. 12.5 18.75 62.5 1.1 4.5 12.5 31.25 62.5 1.6 4.5 71.0 108 11,875 21d 530-- 12.5 31.25 62.5 1.1 4.5 12.5 37.50 62.5 1.6 4.5 85.2 108 12,500 2211 530.-.- 12.5 37.50 62.5 1.1 4.5 12.5 43.75 62.5 1.6 4.5 99.5- 108 13,125 23d 530--.. 12.5 43.75 62.5 1.1 4.5 12.5 50.00 62.5 1.6 4.5 113.5 108 13,750 24d 53c 12.5 50.00 62.5 1.1 4.5 12.5 62.50 62.5 1.6 4.5 142.0 108 15,000 25d 62c 10.84 75.88 1.5 7.0 10.84 5.42 75.88 1.5 7.0 12.31 130.9 10,298 26d 62d- 10.84 5.42 75.88 1.5 8.0 10.84 10.84 75.88 1.5 7.0 24.62 130.9 ,840 27d 62t: 10.84 10.84 75.88 1.5 7.0 10.84 16.26 75.88 1.5 7.0 36.90 130.9 11,382 28d 620."- 10.84 16.26 75.88 1.5 7.0 10.84 21.68 75.88 1.5 7.0 49.3 130.9 11,924 2911 62c 10.84 23.28 75.88 1.5 7.0 10.84 27.10 75.88 1.5 7.0 61.6 130.9 12,466 30d 620-... 10.84 27.10 75.88 1.5 7.0 10.84 32.52 75.88 2.0 7.0 73.8 130.9 13,008 3111 620-.-- 10.84 32.52 75.88 2.0 7.0 10.84 43.36 75.88 2.0 7.0 98.5 130.9 14,092 32d 62c. 10.84 43.36 75.88 2.0 7.0 10.84 54.20 75.88 2.0 7.0 123.1 130.9 15,176

*Oxylkylation-susceptlble.

TABLE VIII Max. Max. Solubility Ex. temp., pres Time, No. O. p. s. hrs.

Water Xylene Kerosene 15-20 15-20 15-20 1520 15-20 1520 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 1015 10-15 1015 10-15 10-15 10-15 10-15 10-15 15-20 15-20 Emulsifiable- The preferred TABLE -VIH-Contlnued Max Max. Solubility Ex. torn pres, Time, No. p. s. 1. hrs.

Water Xylene Kerosene 15-20 15-20 15-20 15-20 15-20 15-20 6 15-20 1 15-20 1% 115-20 2 15-20 3% 15-20 3% 15-20 4 39 125-130 15-20 5 400 125-130 15-20 41 125-130 15-20 1% Insoluble. 42: 125-130 15-20 1 Dlsperslhle. 43c 125-130 -20 2 Soluble. 44 125-130 15-20 3 D0. 45c 125-130 15-20 4 460. 125-130 15-20 3 m. 125-130 15-20 4 480" 125-130 15-20 5 D0.

125-130 -35 Insoluble. 125-130 25-35 1% Dlsperslble 125-130 25-35 2 D0. 125-130 25-35 3 Soluble. 125-130 25-35 4 o. 125-130 25-35 3% D0. 125-130 25-35 4 Do. 125-130 25-35 5 D0. v130-135 5-10 2 Insoluble 130-135 5-10 2% Dlsperslhle 1130-135 5-10 215 D0. 130-135 5-10 3 Soluble. 130-135 5-10 4 D0. 130-135 5-10 4 D0. 130-135 1 '5-10 415 Do. 1 130-135 -5-10 5 D0.

1.25-135 15-20 Insoluble. 125-135 15-20 1; Do. 125-135 15-20 1 Dlsperslble. 125-135 15-20 2 oluble. 125-135 15-20 13 Do. 125-135 1'5-20 2 ,5 Do. 125-1 15-20 :3 D0. 125-135 15-20 4 Do. I

125-130 15-20 $4 Insoluble 125-130 15-20 1 Do. 125-130 15-20 1 D0. 125-130 15-20 2 Disperslble. 125-130 15-20 3 oluble. 125-130 15-20 3 D0. 125-130 15-20 3% Do. 125-130 15-20 4 Do. 125-130 15-20 Insoluble 125-130 15-20 A Do. 125-130 15-20 D0. 125-130 15-20 Do. 125-130 15-20 D0. 125-130 15-20 D0. 1.25-1.30 15-20 Disperslble. 125-130 15-20 Soluble. 125-130 15-20 Insoluble. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 Do. 125-130 15-20 Disperstble 125-130 15-20 oluble. 125-130 25-30 Do. 125-130 25-30 D0. 125-130 25-30 D0. 125-130 '25-30 Dlsperslble. 125-130 25-30 Insoluble. 125-130 25-30 Do. 125-130 25-30 D0. 125-130 25-30 5 D0. 130-135 5-10 Soluble. 130-135 5-10 D0. 130-135 5-10' D0. 130-135 5-10 Do. 130-135 5-10 Dlsperslbla. 130-135 5-10 Insoluble. 130-135 5-10 D0. 320 130-135 5-10' D0.

, oxyalkylatlon wlth a monoepoxlde 1t 1s usually necessary PART 8 to use a catalyst as prevlously descrlbed and, thus, there The res1n condensates whlch are employed as lntermemay be or may not be sufiiclcnt catalyst present for the dlate reactants are strongly bas1c. Inrual oxyalkylatlon reactlon wlth the dlepoxlde. Reference to the catalyst of these products wlth a monoepoxlde or dlepoxlde elther 7, present lncludes the re dual catalyst [emmmng f h one can be accompllshed generally, at least 1n the lnltlal oxyalkylatlon step 1n whlch the monoepoxlde was used.

1 4O stage, wlthout the addulon of the usual alkyllne catalyst Brlefly stated then, employlng polyepoxldes 1n comsuch as those descrlbed 1n connectlon w1th oxyalkylatlon blnatlon wlth a nonbaslc reactant the usual catalysts inenlploylng monoepoxldes 1n Part 7 lmmedlately precedclude alkallne materlals, such as caustlc soda, caustic mg. As a matter of fact, the procedure 13 substantlally potash, sodlum methylate, etc. Other catalysts may be the same as uslng a non-volatlle monoepoxlde such as 2101010 1n nature and are of the klnd illustrated by iron glycide or methyl-glycide. However, during progressive and tin chloride. Furthermore, insoluble catalysts such 33 as clay or specially prepared mineral catalysts have been used. rapidly enough with the dig'iycidyl ether or other analogous reactant then a small amount of finely divided If for any reason the reaction does not proceed 34 of xylene. The initial addition 1:. the diepoxide solution was made after raising the temperature of the reaction mass to about 105 C. The diepoxide was added slowly over a period of one hour. During this time the tern 5 a caustic soda or sodium methylate can be employed asa perature was allowed to rise to about 126 C. The mixcatalyst. The amount generally employed would be 1% ture was allowed to refiux at about 132 C. using a phaseor 2%. separating trap. A small amount of xylene was removed It goes without saying that the reaction can take place by means of a phase-separating trap so the refluxing temin an inert solvent, i. e., one that is not oxyalkylation-sus- Perfltllre I056 gradually to about T mixture ibl G ll ki hi i t i tly was refluxed at this temperature for about 4 hours. At the an aromatic sglvent uch as xylene ra higher boiling end Of this period the xylene Which had been removed coal tar solvent, or else a similar high boiling aromatic y means of the Phase-Separating p Was mtumfid to the solvent obtained from petroleum. One can employ an mixture- A Small amount of mammal was wlthdlawn oxygenated solvent such as the diethylether of ethyleneand the Xylene evaporated a hot Plate Order to glycol, or the diethylether of propyleneglycol, or si iexamine the physical properties. The material was an lar ethers, either alone in combination with a hYdIoamber, or reddish amber, viscous liquid. It was insoluble carbon solvent. The selection of the solvent depends in in Water; it was ins1ub1e in glucfnic acid; but It was part on the subsequent use of the derivatives or reaction Soluble m Xylene and pamculafly m Him/Lure of 7 products. If the reaction products are to be rendered Xylene and methanol However 1f the mammal solvent-free and it is necessary that the solvent be readily was dlssolved Wg solvent aI 1d then shaken removed as f example, by the use of Vacuum disti11a w1th 5% glucomc acld it showed a definite tendency to tion, then xylene or an aromatic petroleum solvent will dlsperse suspend form a and amcularly serve. If the product i going to be subjected to xylene-methanol m1xed solvent as prevlously described, alkylation subseq tl h the Solvent should be one with or without the further addition of a little acetone. which is not oxyalkylation-susceptible. It is easy enough Genera Speakmgithe solublhty of i denvauves to select a suitable solvent if required in any instance but, hue wlth i by 1y examming the solu. everything else being equal, the solvent chosen should be blmy of Precedmg mtemiedlates to oxythe most economical one alkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from ex- Example 1e tremely water-soluble products due to substantial oxyj ethylation, to those which conversely are water-insoluble f was obtalPed by reacuol'l between the but xylene-soluble or even kerosene-soluble due to high epoxlde Prev ously described as diepoxide 3A and oxystage oxypropylation. Reactions with diepoxides or polyalkylated resin condensate 1c. Oxyalkylated cond epoxides of the kind herein described reduce the hydrolc has been described in previous Part 7 and was obtained 0 hfl properties d increase the hydrophobe properties, y the y ylatlon of condensate 1b. The P p i. e., generally make the products more soluble in kerotion of condensate lb was descrlbed in Part 6, preceding. Sena or a i t e of kerosene and xylene, or in xylene, Detalls have been Included to both P but less soluble in water. Since this is a general rule delfsate tum, Y Obtalned from dlethylflmine and which applies throughout, for sake of brevity future refresm 2a; resin 2a, in turn, was obtained from paracreme t solubility will be omitted, tertlal'ybutylphenol and formaldehyde- The procedure employed, of course, is simple in light 111 any evellt, grams of the oXyalkylated resin (1011- of what has been said previously and in effect is a prodensate prevlously identified as 1c were dissolved in apcedure similar to that employed in the use of glycide or proximately an equal weight of xylene. About 2 grams of methylglycide as oxyalkylating agents. See, for example, sodium methylate were added as a catalyst so the total Part 1 of ,U. S. Patent No. 2,602,062, dated July 1, 1952, amount of catalyst present, including residual catalyst to De GIOOtefrom the prior oxyalkylation, was about 2.4 grams. 17 Various examples obtained in substantially the same grams of diepoxide 3A were mixed with an equal weight manner are enumerated in the following tables:

, TABLE 11:

Ex. Qxy. Amt., Diep- Amt., Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOOHz), lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. C.

223 3A 17 2. 4 240 2:1 4 150 Viscous reddish amber mass. 375 3A 17 3.9 392 2:1 4 148 Do. 271 3A 8. 5 2.8 230 2:1 4 145 Do. 377 3A 8. 5 3. 9 386 2: 1 4 142 Do. 113 3A 1. 7 1. 2 115 2: 1 3 Do. 335 3A 17 3. 5 352 2:1 4 Do. 375 3A 17 3.9 392 2:1 4 143 D0. 271 3A 3. 5 2.8 280 2: 1 4 146 Do. 314 3A 8. 5 3, 2 323 2: 1 4 Do. 363 3A 8. 5 3. 7 372 2:1 4. 5 150 Do. 391 3A 17 4.1 408 2: 1 4. 5 152 Do. 279 3A 8. 5 2. 9 288 2: 1 4 148 Do. 353 3A 8. 5 3. 7 372 2; 1 4. 5 150 Do. 100 3A 1. 7 1.0 102 21- 3 150 Do. 152 3A 1. 7 1. 5 154 2:1 4 152 Do.

Color and physical 'state perature of reaction by Ily'lower boiling solvent, e entirely. Also, we have use slightlyless than ap- Max. te mp 153 Viscous reddish amber mass.

1 reaction,

' hrs.

Molar Timep't ratio ethylether .ot ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the tern adding a small amount of initia such as benzene, or use benzen found it desirable at times -to parently the theoretical .amou

Xy- I lene,' ITS.

mmammmwmammmmmm TABLE X Catalyst (N39011:), grs.

solvent The condensate can be depicted in a sim which, for convenience, may be shown'thus:

stance, 90% to 95% ular weight by several percent.

mmmmmmmmmwmmm 1n I LLLLLLLLZL solvent e -t mum Wm fm sd s \I S n n u 0 9 a m .m a m mm a wmmdm 1. an H HIVAVH C w md h fi m m m m m a m l .m u v R RSYMM a n m t. M a P v. n o. n a t u m m D n w a & 0h n We .6 r e e w w t m :emUW H HT w w p m c e e pu .m m G e w m m e a I a a m P h n o .m n wMcP m .m m

0 85000 0 55 zmmmmmmnnmmnmmn LZLLLLO- LLL-LLLLL Amt. grs.

Amount of Amount of product, grs.

7 0005000005 000 4 4 9 I a rlwzmmu Amount of Amount of product, grs.

m mwwm 88 4. 4. 7 5

TABLE XI Prob. mol weight of reaction product Amt, grs.

1 mean nnmmam n n nmn nnmm TABLE 'XII Prob mol. weight of Ieaction product 0 00 0o 0 mwwcmmomnmmnmmm nwn nnw nwww densate v Oxyalkyl. resin-com Oxyalkyl. resin con- .densate Ex, No.

Ex. No.

Ex. N o.

of what has been said previously:

[(Amine)CH,(Resin)] This product, since it is susceptible to oxyalkylation by means of the oxyalkylated phenolic hydroxyl groups and depending on the selection of the amine, may be susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[Oxyalkylated(Amine)CH,( Resin) When a diglycidyl ether is employed one would obviously obtain compounds in which two molecules of the r kind described immediately preceding are united in a manner comparable to that previously described, which may be indicated thus:

OxyalkylateMAminemH;(Resin) D.G.E.

Oxyalkylated(Amine)CH1(Resiri) Likewise, it is obvious that the two different types of At this point it may be desirable to direct attention to two facts, the first being that we are aware that other diepoxides free from an aromaic radical as, for example, epoxides derived from ethylene glycol, glycerin, or the like such as the following:

may be employed to replace the diepoxides herein de- 6 scribed. However, such derivatives are not included as part of the instant invention.

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient crossdinking or gelling even when the molal ratio is in the order of 2' 7 We have found this can be avoided by any one of the following procedures or Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the dimoles of resin to one of ,diepoxide.

their equivalent.

. r 37, oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

l(AInine)OHz(xyalkylated Resin)OHz(Amine:

til

I i (Amine) CH2(Oxyalkylated Resin)CH (Amine) oxyalkylated (Amine) GHKAmine) l l l' l oxyalkylated (Amine)CH2(Resin) Oxyalkylated (Amine) CH2 (Amine) l l l' l Oxyalkylated (Amine) 0 H1 (Amine) PART 9 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution'with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection witn conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since .such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or '1 to 50,000 as in desalting practice, such an apparent iinsolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including 38 batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 3e with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

oxyalkylated derivative, for example, the product of Example 3e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 10 The products, compounds, or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the waterin-oil type as described in detail in Part 9, preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropanc of the structure.

wherein R and R" are alkyl groups.

It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 5, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 7, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc'.

They may The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose .of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly 'in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; .as additives for lubricants, both of the natural petroleum type and the synthetic type,

as additives in the flotation of ores, and at times as-aids in chemical reactions insofar that demulsification is produced between the 'insoluble'reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

The products herein described can be reacted with polycarboxy acids, such as phthalic acid or anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives, particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical present in the .final polyepoxide-treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum .emulsions of the water-in-oil type .as herein described.

Having thus described .our invention what we claim as new and desire to secure by Letters Patent is:

1. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide containing at least two 1,2-epoxy rings; said first manufacturing step being a method of (A) condensing, (a) a fusible, non-oxygenated organic solvent-soluble, water-insoluble, phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having up to 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted .at a .temperature'sutficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable; followed as a second step by (B) oxyalkylation :by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the .40. class consisting of ethylene oxide, propylene Oxide, butylene oxide, glycide and methylglyeide; and then oompleting the reaction by a third step of (C) reacting said oxyalkylated resin condensate with a phenolic polyepoxide free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and .eogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the atetramers; said polyepoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which .2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by-the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent the divalent radical, the divalent sulfone radical, and divalent monosulfide radical S-, the divalent radical --CH,SCH,, and the divalent disulfide radical S S; said phenolic portion of the polyepoxide being obtained from a phenol of the structure product be a member of :the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction :between the ,monoepoxide oxylkylated resin condensate and iaryl diepoxide he conducted below the pyrolytic point of the reactants .and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the ,oxyalkylated resin condensate to '1 mole of the :phenolic-polyepoxide.

2. The method of claim 1 wherein the precursory phenol contains at least 4 and not over 14 carbon atoms in the substituent radical and the precursory aldehyde is formaldehyde.

3.. The product obtained .by the method described in,

claim 1.

4. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalk-ylation 'with a diepoxide; said first manufacturing step being a method of (A) condensing (a) a fusible, non-oxygenated organic solvent-soluble, waterinsoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in-regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an .aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of .the formula 

1. A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING, (A) A FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 